CN1428293A - Catalyst for low-temp. selective oxidation of CO in hydrogen gas and its preparation method - Google Patents
Catalyst for low-temp. selective oxidation of CO in hydrogen gas and its preparation method Download PDFInfo
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- CN1428293A CN1428293A CN 01138913 CN01138913A CN1428293A CN 1428293 A CN1428293 A CN 1428293A CN 01138913 CN01138913 CN 01138913 CN 01138913 A CN01138913 A CN 01138913A CN 1428293 A CN1428293 A CN 1428293A
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Abstract
The catalyst for low-temp. selection and oxidation of CO being in hydrogen gas is formed from carrier and active component. The SiO2, Al2O3, TiO2, active carbon or molecular sieve can be used as carrier, and the metal copper or silver single component or two-component metal formed from one of copper and silver and platinum can be used as active component, in which the metal is 0.5-30% of weight percentage of carrier, and the weight ratio of two metal elements of copper or silver and platinum in two-compoent metal is 16:1-8.
Description
Technical field
The present invention relates to the catalyzer of selectivity oxidizing carbon monoxide in the hydrogen, specifically a kind of Catalysts and its preparation method that is used for low temperature selective oxidation hydrogen CO.
Background technology
In recent years, the fuel cell (PEFC) that with hydrogen is fuel is in light weight because of it, volume is little, do not produce secondary pollutant, have characteristics such as high energy utilization rate at low temperature and be widely studied and applied, fuel cell more and more be it is believed that it is the energy derive of ideal motor vehicle, semiworks etc. in the future.For fear of storing highly compressed hydrogen onboard, and be used to produce the hydrogen of the energy mainly from methyl alcohol and hydro carbons; Fuel cell need come cryogenic oxidation of hydrogen of catalysis and oxygen reduction with the platinum electrode catalyzer, but platinum electrode is easy to be polluted by a small amount of incomplete combustion product carbon monoxide at a lower temperature, thereby make the utilization ratio of fuel cell reduce [S.Gottesfeld, J.Pafford, J.Electrochem.Soc.135 (1988) 2651]; Mainly address this problem at present from two aspects, the one, solve the ability of the anti-carbon monoxide of Pt electrode, the 2nd, reduce the content of carbon monoxide as far as possible, from the catalysis angle and handle on the complexity, second method is easier; That is petty in the method for various reduction carbon monoxide contents, and it is the simplest and inexpensive method that the catalyzed oxidation of carbon monoxide is eliminated; The catalyzer that people study maximum CO selective oxidations is Al
2O
3The Pt that supports, Rh, noble metal catalysts such as Ru.Pt/Al
2O
3Catalyzer is studied at first, but it needs the oxygen of unnecessary metering ratio in reaction, and this may cause the danger of instantaneous blast and the unnecessary consumption of hydrogen, reduce rate of energy [M.J.Kahlich, H.A.Gasteiger, R.J.Behm, J.Catal.171 (1997) 93].The Ru-mordenite catalyzer has 100% selectivity to carbon monoxide, but the temperature that it need be very high [H.Igarashi, H.Uchida, M.Watanabe, Chem.Lett. (2000) 1262].The Au catalyst that metal oxide supports is the optional catalyzer of the low temperature elimination of carbon monoxide, Au/Al
2O
3Catalyzer is 100 ℃ of selectivity with carbon monoxide oxidation of 50%, the size of particles of gold is greatly about 5～10nm[G.K.Bethke, H.H.Kung, Appl.Catal.A 194 (2000) 43] its weak point is: cost of material is higher, and catalyst selectivity is lower.
With regard to the catalyzer of selectivity oxidizing carbon monoxide in the hydrogen, require it can eliminate a spot of carbon monoxide at a lower temperature, but do not lose hydrogen, promptly require catalyzer that higher selectivity will be arranged; If CO and O
2In reaction gas, exist, and fully with hydrogen balance, that petty this research then has more challenge with chemical ratios, because amount of oxygen increases, though can improve the transformation efficiency of carbon monoxide, hydrogen also is consumed simultaneously, selectivity also and then descends, and this will reduce the utilising efficiency of fuel cell; Silver is as a kind of oxide catalyst preferably, it successfully has been used for the reaction of ethylene epoxidizing, and the low-temperature oxidation for carbon monoxide also has active preferably [G.G.Xia, Y.G.Yin, W.S.Willis et al.J.Catal.185 (1999) 91], up to the present also be not advantageously applied to the carbon monoxide in the selective oxidation hydrogen.
Summary of the invention
The object of the present invention is to provide a kind of energy utilization rate height, the Catalysts and its preparation method that is used for low temperature selective oxidation hydrogen CO that selectivity is also high.
To achieve these goals, catalyzer of the present invention is made up of carrier and active ingredient, with SiO
2, Al
2O
3, TiO
2, gac or molecular sieve be carrier, one of metallic copper or silver-colored single component or copper and silver are active ingredient with the two-pack metal of platinum, wherein to account for the weight percent of carrier be 0.5～30% to metal;
In above-mentioned catalyzer, the mass ratio of two kinds of metallic element copper or silver-colored and platinum is 16: 1～8 in the wherein said two-pack metal;
The method for preparing catalyst that wherein said activity of such catalysts component is the single component metal has two:
1. pickling process: its concrete preparation process is: at first with the precursor dissolving of single component metal, incipient impregnation is on carrier; Room temperature was dried in the shade 8～16 hours then, 80～120 ℃ of oven dry; Before reaction with above-mentioned catalyzer at oxygen, carried out necessary in-situ treatment under hydrogen or the helium-atmosphere 2～4 hours, temperature is 100～700 ℃.
The precursor of wherein said metal (flooding used salt) is the nitrate of Cu, Ag, Cu (Ph
3P) NO
3Perhaps Ag (Ph
3P) NO
3
2. micro emulsion method: its concrete preparation process is: tensio-active agent (as: polyoxyethylene (n=2-20) lauryl ether, five ethene glycol lauryl ethers, 2-ethylhexyl sulfo-Soduxin, polyoxyethylene nonyl phenylate etc.) be dissolved in the mixed solution of hexanaphthene and propyl carbinol, the volume ratio of propyl carbinol and hexanaphthene is 1: 4～6 in the described mixed solution, the aqueous solution that under vigorous stirring, adds a certain amount of single component metal-salt, stir and form micro emulsion, regulate mol ratio W=1～15 of water and tensio-active agent simultaneously, to obtain the metallics of different size; Add hydrazine hydrate after stirring 1～2h, stir 2～3h, adding proper ammonia adjusting pH value is 8.5-11, adds TEOS (tetraethoxy) and hexanaphthene at last, and the weight ratio that makes TEOS and hexanaphthene is 1: 1～6, and mixture stirred 2～5 hours; After filtration, washing is dried sample, 300～700 ℃ of roastings 2～5 hours under 80～120 ℃ of air;
This micro emulsion method also can add SiO behind the described therein formation micro emulsion
2, add hydrazine hydrate again after stirring, after filtration, washing, the sample of acquisition was dried under 80～120 ℃ of air, 300～700 ℃ of roastings 2～5 hours;
Salt used in the wherein said micro emulsion method can be nitrate;
In addition, before reaction with above-mentioned catalyzer at oxygen, handle 2～4h in hydrogen or the helium, temperature is 100～700 ℃;
Wherein said activity of such catalysts component is the method for preparing catalyst of two-pack metal: operating process is: with the aqueous solution of the two-pack metal-salt of solubility, method with dipping is supported on the carrier, dipping copper or silver after elder generation's platinum-impregnated, sample after supporting is 80～120 ℃ of oven dry, 450～600 ℃ of roasting 2～4h in the air, afterwards under reducing atmosphere 300～600 ℃ the reduction 1～4 hour;
Wherein said metal-salt (precursor of dipping) is CuNO
3, AgNO
3And H
2PtCl
66H
2O;
Wherein said Application of Catalyst, concrete reaction conditions is: reaction gas is formed 1%CO, 0.5%O
2, H
2Balance, reaction pressure normal pressure, temperature of reaction-80～250 ℃.
The present invention has following advantage:
1. catalyst performance is good.Catalyzer of the present invention has good stability at low temperature, and it has higher activity and selectivity at low temperature; In the hydrogen in the CO selective oxidation reaction, temperature of reaction can be reduced to subzero single component catalyst among the present invention under cold condition, and cryogenic selectivity can reach 70～95%, and the transformation efficiency of CO maximum approximately is 50%; This catalyzer is eliminated in the reaction at pure CO simultaneously also good active, and CO just can reach 50% conversion at 5 ℃.
2. the catalyzer cost is lower.Catalyzer of the present invention is easy to preparation, and price is lower, greatly reduces the cost of catalyzer, and good application prospects is arranged.
3. energy utilization rate height.Catalyzer of the present invention is in application process, and reaction does not need the oxygen of unnecessary metering ratio, CO and O
2Exist with chemical ratios in reaction gas, security is good, improves the energy utilization rate of catalyzer.
Description of drawings
Fig. 1 is SiO
2The XRD spectra of the catalyzer of the different silver contents that support after 500 ℃ of helium are handled 2h.
Fig. 2 a is SiO
2Oxygen transforms and the pairing temperature variation collection of illustrative plates of CO maximum conversion rate fully in the reaction of the different silver that support, bicomponent catalyst CO in low temperature selective oxidation hydrogen of platinum mass ratio.
Fig. 2 b is SiO
2Selectivity ratios in the reaction of the different silver that support, bicomponent catalyst CO in low temperature selective oxidation hydrogen of platinum mass ratio under the differing temps is than collection of illustrative plates.
Embodiment
Embodiment 1
Adopt equi-volume impregnating to prepare SiO
2The silver catalyst of load.Be dissolved in 8 ml distilled waters by the part by weight of active ingredient and carrier Silver Nitrate, to wherein adding 5 gram SiO 0.1575g
2Carrier stirs the back and placed 12 hours in room temperature, 80 ℃ of oven dry, and the loading that obtains silver is the supported catalyst of 2wt%; The loading that adopts identical method can obtain silver is respectively 4wt%, 6wt%, 8wt%, 12wt%, the catalyzer of 16wt%, its under helium 500 ℃ handle 2h after, active ingredient silver mainly exists with the form of metal.As shown in Figure 1, the size of metallic silver corpuscle increases along with the increase of the loading of silver.
Adopt pickling process with Ag (Ph
3P) NO
3Be precursor, SiO
2Catalyzer for preparing carriers.Take by weighing 6g Ph
3P joins in a certain amount of methyl alcohol, and 50 ℃ of following stirring and dissolving, the 5.02g Silver Nitrate is dissolved in a spot of methyl alcohol and the acetonitrile, under stirring state the solution of Silver Nitrate is all joined Ph afterwards
3In the P solution, behind the reaction 2h, drop under the room temperature and react 8h, be put into refrigerator overnight (10～-4 ℃, 8～12 hours) at last, prepare Ag (Ph
3P) NO
3Precursor; Weight ratio by active ingredient and carrier takes by weighing 0.35g Ag (Ph
3P) NO
3Be dissolved in a spot of acetone and the acetonitrile, add 2g SiO to it
2Carrier, the room temperature solvent flashing, 80 ℃ of oven dry, obtaining loading is the silver-colored supported catalyst of 4wt%, 350 ℃ of roasting 4h in retort furnace.
Embodiment 3
Adopt prepared with microemulsion reactor Ag/SiO
2Catalyzer.Take by weighing 6g (after the concentration of salts solution was determined, promptly the mole number of water was definite, and its value changes according to the w value) tensio-active agent (C
16H
33(OCH
2CH
2)
nOH, n=2～20),, add afterwards and contain 0.06g AgNO to wherein adding the dissolving of 20ml hexanaphthene and 5ml propyl carbinol
33.6 milliliters of the aqueous solution (w=4) stir and form microemulsion; Add two hydrazine hydrates (85%), reduction AgNO
3Add ammoniacal liquor, regulate PH=9; Add 3.57g TEOS afterwards, the mixture of 4ml hexanaphthene and water stirs and makes TEOS hydrolysis formation SiO
2, aging, to filter, washing forms Ag/SiO
2Sample.After forming microemulsion, can add ready-made SiO in addition
2Carrier stirs 2h, adds two hydrazine hydrates afterwards, makes deposition of silver at SiO
2On the carrier, all the other operations are the same.
According to silver, the weight ratio of platinum takes by weighing a certain amount of H respectively
2PtCl
66H
2O is dissolved in the 3.2ml water, to wherein adding 2g SiO
2, the AgNO of 0.5039g is flooded in 120 ℃ of oven dry again
3The aqueous solution, 80 ℃ of oven dry, 500 ℃ of roasting 4h in retort furnace reduce 90min before the reaction under 400 ℃ of hydrogen atmospheres.Silver, platinum mass ratio are 16: 2,4,6,8.Bimetal silver, the platinum supported catalyst can pass through graded impregnation, as elder generation's silver back platinum, or silver behind the first platinum, also can use co-impregnation; The better catalytic activity of the catalyzer that silvery is equipped with behind the experiment confirm elder generation platinum.
Embodiment 5
Ag/SiO
2The silver loading was with the influence of temperature to reactivity worth when supported catalyst was used for low temperature hydrogen CO selective oxidation reaction.The silver loading is respectively: 2wt%, 4wt%, 6wt%, 8wt%, 12wt%, 16wt%, 20wt%.Take by weighing the catalyzer of the different loadings of 0.25g 40～60 purposes, the reaction procatalyst is handled 2h through helium at 500 ℃; Reaction gas consists of 1%CO, 0.5%O
2And 98.5%H
2, flow velocity is 50ml/min.Concrete outcome is as shown in table 1: the Ag/SiO of the different loadings of table 1
2Catalyzer under cold condition in the hydrogen activity of CO selective oxidation and selectivity silver loading oxygen change the temperature inversion rate (%) that the CO the highest conversion the highest cryogenic selective of CO (wt%) is changed the temperature correspondence fully
(℃) (℃) (％)
2 120 90 8.48
4 100 70 16.13
6 80 60 23.35
8 60 50 31.06 70～90
12 45 38 35.9
16 40 35 38.89
20 38 38 37.22
Oxygen transform fully and CO the temperature of high conversion reduce along with the increase of silver-colored loading, the conversion rate curve of the CO oxidation of all catalyzer is parabolic type, the CO peak rate of conversion increases along with the increase of silver-colored loading, the selectivity of selective oxidation reduces along with the rising of temperature, illustrate that this catalyzer is the optional catalyzer of low temperature CO selective oxidation, cryogenic selectivity can reach 70～90%.
Ag/SiO
2Catalyzer is used for low temperature hydrogen CO selective oxidation reactive activity along with variation of temperature after 500 ℃ of oxygen are handled 2h.Take by weighing the 0.25g catalyzer, the loading of silver-colored active ingredient is 16wt%.1%CO, 0.5%O
2With the flow velocity of the gas mixture of 98.5% hydrogen be 50ml/min, temperature of reaction is from 0 ℃ to 100 ℃, concrete outcome sees Table 2.Table 2 16wt%Ag/SiO
2CO in the hydrogen under the cold condition of catalyzer after 500 ℃ of oxygen are handled 2h
The selective oxidation reactive activity
Oxygen changes the highest conversion of the CO the highest CO of the highest conversion CO fully
Change the temperature correspondence temperature inversion rate rate correspondence select cryogenic selective
(℃) (℃) (%) selecting property (%) is (%)
50 45 40.56 44.14 80～90
Take by weighing the 0.1575g Silver Nitrate and be made into the 8ml aqueous solution, to wherein adding the SiO of 5g through 700 ℃ of roasting 10h
2Carrier, all the other operational conditions are with embodiment 1.The silver loading is 2wt%.Take by weighing this catalyzer of 0.25g, the reaction procatalyst is used hydrogen subzero treatment 1h, 1%CO, 0.5%O again through oxygen pyroprocessing 2h
2With the flow velocity of the gas mixture of 98.5% hydrogen be 50ml/min.Concrete outcome is shown in Table 3: table 3 2wt%Ag/SiO
2Catalyzer is through oxygen pyroprocessing 2h, and low temperature hydrogen is handled the low temperature bar behind the 1h
CO selective oxidation reactive activity in the hydrogen under the part
Oxygen changes the highest conversion of the CO the highest CO of the highest conversion CO fully
Change the temperature correspondence temperature inversion rate rate correspondence select cryogenic selective
(℃) (℃) (%) selecting property (%) is (%)
50 45 48.87 52.78 90～95
Catalyzer has very high reactivity and selectivity at low temperature, and the peak rate of conversion of carbon monoxide is 48.87%, and its corresponding selectivity is 52.78%, and cryogenic selectivity is 90～95%.
The silver when loaded catalyst of silver, platinum two-pack is used for low temperature hydrogen CO selective oxidation reaction, the platinum mass ratio is to the influence of reactivity worth.The silver loading is 16wt%, and the loading of platinum is respectively 2wt%, 4wt%, and 6wt%, 8wt% takes by weighing 0.25g 40～60 purpose supported catalysts, and the reaction procatalyst is handled 90min, 1%CO, 0.5%O for 400 ℃ through hydrogen
2With the flow velocity of the gas mixture of 98.5% hydrogen be 50ml/min, from 20 to 150 ℃ of temperature of reaction.Its concrete outcome as shown in Figure 2, the temperature that CO peak rate of conversion and oxygen transform fully raises along with the increase of platinum content, and corresponding selectivity also increases along with the increase of platinum content under same temperature.
When embodiment 5～8 catalyzer were used for low temperature hydrogen CO selective oxidation reaction, concrete reaction conditions is: reaction gas was formed 1%CO, 0.5%O
2, H
2Balance, reaction pressure normal pressure, temperature of reaction-80～250 ℃, flow velocity 50ml/min.
Relevant comparative example:
5%Pt/Al
2O
3Catalyzer: 1%CO, 1～2%O
2, 75%H
2, N
2Balance, the starting temperature of reaction are 100 ℃, and the highest invert point of CO is 200 ℃, and peak rate of conversion is 80%, and corresponding selectivity is 40%.
Ru-mordenite catalyzer: 1%CO, 0.5%O
2, H
2Balance, 200 ℃, catalyzer can reach 100% transformation efficiency.
Au/Al
2O
3Catalyzer: prepare with deposition-precipitation method; Reaction gas consists of 1%CO, 0.5%O
2, 48%H
2, He balance, 100 ℃ of selectivity with carbon monoxide oxidation of 50%.
Compared with prior art the catalyzer among the present invention just has very high selectivity to CO in the hydrogen at normal temperatures, can reach 70～90%, and CO is at the transformation efficiency of 40 ℃ of left and right sides Ke Da 40～50%, and its corresponding selectivity is about 50%; And Au catalyst [Appl.Catal.A 194 (2000) 43], 100 ℃ of selectivity with carbon monoxide oxidation of 50%; Pt, Ru catalyzer [Chem.Lett. (2000) 1262] is in the reactionless at all activity of low temperature.
Claims (10)
1. a catalyzer that is used for low temperature selective oxidation hydrogen CO is made up of carrier and active ingredient, it is characterized in that with SiO
2, Al
2O
3, TiO
2, gac or molecular sieve be carrier, one of metallic copper or silver-colored single component or copper and silver are active ingredient with the two-pack metal of platinum, wherein to account for the weight percent of carrier be 0.5～30% to metal.
2. catalyzer according to claim 1 is characterized in that in the wherein said two-pack metal that the weight ratio of two kinds of metallic element copper or silver and platinum is 16: 1～8.
3. Preparation of catalysts method according to claim 1 is characterized in that concrete preparation process is: at first with the precursor dissolving of single component metal, incipient impregnation is on carrier; Room temperature is dried in the shade then, 80 ℃～120 ℃ oven dry; Before reaction, will dry product at oxygen, carry out in-situ treatment in hydrogen or the helium-atmosphere.
4. Preparation of catalysts method according to claim 3, the precursor that it is characterized in that wherein said metal are the nitrate of Cu, Ag, Cu (Ph
3P) NO
3Perhaps Ag (Ph
3P) NO
3
5. Preparation of catalysts method according to claim 1, it is characterized in that concrete preparation process is: with surfactant dissolves in the mixed solution of hexanaphthene and propyl carbinol, the volume ratio of propyl carbinol and hexanaphthene is 1: 4～6 in the described mixed solution, the aqueous solution that under vigorous stirring, adds a certain amount of single component metal-salt, stir and form micro emulsion, regulate the mol ratio W of water and tensio-active agent, make W=1～15; Under agitation add hydrazine hydrate successively, it is 8.5-11 that proper ammonia is regulated pH value, adds TEOS and hexanaphthene, and the weight ratio that makes TEOS and hexanaphthene is 1: 1～6, stirs 2～5h then; After filtration, washing is dried sample, 300～700 ℃ of roastings 2～5 hours under 80～120 ℃ of air.
6. Preparation of catalysts method according to claim 5 is characterized in that wherein saidly adding SiO after forming micro emulsion
2, add hydrazine hydrate again after stirring, after filtration, washing is dried sample, 300～700 ℃ of roastings 2～5 hours under 80～120 ℃ of air.
7. according to claim 5 or 6 described Preparation of catalysts methods, it is characterized in that wherein said tensio-active agent is polyoxyethylene (n=2-20) lauryl ether, five ethene glycol lauryl ethers, 2-ethylhexyl sulfo-Soduxin or polyoxyethylene nonyl phenylate.
8. Preparation of catalysts method according to claim 1 and 2, it is characterized in that concrete preparation process is: with the aqueous solution of the two-pack metal-salt of solubility, method with dipping is supported on the carrier, dipping copper or silver after elder generation's platinum-impregnated, sample after supporting is 80～120 ℃ of oven dry, 450～600 ℃ of roasting 2～4h in the air, 300～600 ℃ were reduced 1～4 hour under the reducing atmosphere.
9. Preparation of catalysts method according to claim 8 is characterized in that wherein said metal-salt is CuNO
3Or AgNO
3And H
2PtCl
66H
2O.
10. catalyzer according to claim 1 application in the CO selective oxidation in low temperature hydrogen is characterized in that concrete reaction conditions is: reaction gas is formed 1%CO, 0.5%O
2, H
2Balance, reaction pressure normal pressure, temperature of reaction-80～250 ℃.
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|---|---|---|---|
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| CN101791554A (en) * | 2010-03-31 | 2010-08-04 | 福州大学 | Double-loaded nano-Au composite material with function of removing CO at room temperature |
| CN101898149A (en) * | 2010-07-31 | 2010-12-01 | 大连理工大学 | Supported nanometer metallic sliver catalyst with dual functions of adsorption and low-temperature catalysis, and preparation method and application thereof |
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| CN101362089B (en) * | 2007-08-09 | 2012-07-18 | 宜安德株式会社 | Catalyst for removing carbon monoxide, hydrocarbon and particle matter in engine using high-sulfur combustor and preparation method thereof |
| CN102600840A (en) * | 2007-08-09 | 2012-07-25 | 宜安德株式会社 | Catalyst for removing carbon monoxide, hydrocarbons and particulate matters in engine |
| CN101791554A (en) * | 2010-03-31 | 2010-08-04 | 福州大学 | Double-loaded nano-Au composite material with function of removing CO at room temperature |
| CN101898149A (en) * | 2010-07-31 | 2010-12-01 | 大连理工大学 | Supported nanometer metallic sliver catalyst with dual functions of adsorption and low-temperature catalysis, and preparation method and application thereof |
| CN102836714A (en) * | 2012-08-23 | 2012-12-26 | 北京化工大学常州先进材料研究院 | Preparation method used for combining dimethyl carbonate efficient catalysts |
| CN102921431A (en) * | 2012-10-19 | 2013-02-13 | 大连凯特利催化工程技术有限公司 | Catalyst used in oxidative desorption of carbon monoxide in hydrogen and preparation method for catalyst |
| CN102921431B (en) * | 2012-10-19 | 2014-08-06 | 大连凯特利催化工程技术有限公司 | Catalyst used in oxidative desorption of carbon monoxide in hydrogen and preparation method for catalyst |
| CN105312064A (en) * | 2015-06-30 | 2016-02-10 | 金华氟特催化科技有限公司 | Catalyst used for eliminating carbon monoxide in smoke |
| CN105312064B (en) * | 2015-06-30 | 2017-12-01 | 金华氟特催化科技有限公司 | A kind of catalyst for the middle carbon monoxide that removes smoke |
| CN105964308A (en) * | 2016-05-27 | 2016-09-28 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of carrier material for catalyst for sewage treatment |
| CN114213645A (en) * | 2021-12-23 | 2022-03-22 | 淮安巴德聚氨酯科技有限公司 | Bimetallic catalyst for synthesizing pure ethylene oxide polyether and preparation method thereof |
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